Azo coloring matter dyeing wool fast to milling and process for obtaining the same



Patented Aug. 31, 1926.v

UNITED STATES PATENT OFFICE.

JAMES BADLDILEY, JAMES HILL, AND ALBERT RILEY, 0E MANc IEsTER, ENGLAND, AS- SIGNOBS To RRITIsII DYESTUFFS CORPORATION LIMITED, 01? MANCHESTER, ENG- LAND.

AZO COLORING MATTER DYEING WOOL FAST T0 MILLING AND PROCESS FOR OBTAIN ING THE SAME.

No Drawing. Application filed September 21, 1925, Serial No. 57,777, and in England September 17, 1924.

We have invented new azo dyestuffs which dye Wool giving useful shades fast to mill mg. Our new dyestuffs are obtained by preparing a suitable condensation product by the action of formaldehyde on an amine in the form of its hydrochloride, diazotizing this and then combining it with sulphonated azo dye components, in particular with sulphonated pyraz'olones, naphthol and amino naphthol'sulpho acids; The structural formula of the bodies produced is at present unknown.

Anhydro bases from primary-amines and formaldehyde may be obtained in a variety of ways as a reference to the literature will show (for example, British Patent No. 1963/95. German Patents 83544, 93540,

95600, 96851,'96852, 97762, Berichte e3, p.

'250; J. Russ. Phys. Chem. Soc. Vol. 37, p. 1255 and p. 1272; Vol. 44. p. 1196 and p. 1200, and German Patent 308,839), but the simplest and most economical way of .preparing the diazotizable compounds used in carrying out this invention is by the action of formaldehyde on the amine in the form of its hydrochloride. This is illustrated in the example (1) below.

In the German Patent No. 308,839, Nastukoff & Croneberg describe the producdehyde and aromaticamines in the presence of acid, and further state that the diazo compounds ofthese bodies can be developed on vegetable fibre with suitable components, such as ,B-naphthol, salicylic anilides or pyrazolone derivatives. The pyrazolone derivatives here referred to, like the other developers, are unsulphouated products yielding insoluble dyestufis on the fibre. The structural formula given in this patent does not appear correct.

The present invention consists in the discovery that'new dyestuffs which dye wool T in useful shades fast to milling are obtained when anhydro bases of the type defined above-are treated with nitrous acid and then An example of one way in which our inventlon may be earned out Is as follows (a) Preparation of base.

93 parts of aniline are dissolved in 200 parts of water by the addition of 106 parts of hydrochloric acid (86 TW.) so that the solution is faintly acid to Congo paper, To

the solution (at 20 C. or thereabouts) 90 parts of formaldehydesolution (containing 38.7 grams CH O in 100 ccs.) is added. The

solution acquires a deep yellow co or. The

temperature rises to about 60 C. and the clear solution is kept for 24 hours, and then A (6) Preparation of dye.

The base obtained by the above process is dissolved in the equivalent amount of hydrochloric acid (10 per cent solution), or the total reaction liquor may be used as stated above, To the clearsolutionare added 730 parts of hydrochloric acid (10 per cent) and 4,000 parts of water, and the solution is then cooled to 5 C. and diazotiz'ed by the gradual addition of 7 0 parts sodium nitritein the usual way. The diazo solution is then poured into a solution of 254 parts 1-p.' sulpho phenyl 3-methyl 5-pyrazolone made by dissolving the pyrazolone in 3,000

parts water'and 40 parts caustic soda and .adding 160 parts sodium carbonate, the mixshades of the resulting dyestuffs being thereby influenced according to the generally orthoanisidine, meta-nitraniline, thylamine, and the like may be used in this recognized rules. The anhydro bases from B-naphway to vary the shade, the valuable milling 2 properties remaining.

If in the above example instead of the sulphophenylmethylpyrazolone, an. equivalent amount of 1- (2.5-dichlor-4-su1pho) phenyl-3- methyl-5-pyrazolone is used, a dyestufl having similar fastness properties but of a more greenish-yellow shade is obtained. Similarly, 2-naphthol-6-sulphonic acid gives a yellowish-red; 2.8-aminonaphthol-6-sulphonic acid (combined in acid solution) gives a brown, and 2.7-naphthylamine sulphonic acid gives an orange brownr What we claim isc 1. New az'o coloring matters dyeing wool fast to milling in various shades, which can be obtained by diazotizing the condensation product of formaldehyde and a single primary aromatic amine and combining with sulphonated azo dye components.

2. Azo coloring matters dyeing wool fast to milling, which can be obtained by com- 20 bining the condensation product of aniline with formaldehyde, with a sulphonated phenyl-methyl-pyrazolone.

3. The process of manufacturing azo col oring matters by preparing a diazotizable compound by the action of formaldehyde on a single primary aromatic amine in the form of its hydrochloride, diazotizing this and then combining it with a sulphonated azo In testimony whereof we have hereunto afiixed our signatures.

JAMES BADDILEY.- JAMES HILL. ALBERT RILEY. 

